The preparation of amines plays a crucial role in the synthesis of natural products, polymers, and pharmaceuticals. Therefore, ongoing efforts in modern organic synthesis includes the development of novel catalytic methods that could streamline their preparation, including functionalization of π-systems. Carboamination is one of the most powerful π-functionalization strategies for the synthesis of amines, as it results in a formation of C—C and C—N bonds with high atom- and step-economy. The last decade has seen significant developments in this area, and now several classes of these processes exists for alkenes, alkynes, and dienes. Aromatic compounds could also be considered as viable substrates, especially when considering their availability and the synthetic versatility of the corresponding unsaturated products. However, due to their characteristic stability and reactivity, dearomative carboamination of arenes is virtually nonexistent. Only transition-metal-catalyzed ring-opening of azabicyclic alkenes can provide products resembling those of a formal dearomative carboamination (Scheme 1A, Rayabarapu, D. K.; et al, Acc. Chem. Res. 2007, 40, 971). However, these reactions require more elaborate, benzyne-derived starting materials and cannot provide products resembling those obtained from mononuclear arenes.
Synthetic challenges often present problems that could be solved through better methods, which produce key intermediates with good control of regio- and stereochemistry that are desirable for the synthesis of natural products and drug candidates. Thus, a practical solution to dearomative carboaminations from arenes would provide access to key intermediates that simplify the synthesis of targeted organic molecules.